Copperable disazo dyestuffs



Patented Feb. 23, 1954 GOPPE-RABLE" DISAZU DYESTUFFS" Werner floss ard ltiiehen, near Easel, Switzerland,

assignor to" J. Geigy A.- G.,v Basel, Switzerland, a Swiss firm No Drawing. Application=January 21; 1952 Serial No; 267,502

cams snowy a plication swiaeaans February 7', 1951 .T he' present invention concerns the production of copperabledisazo dyestuiis char'acterisedjby their very good drawing power on to cellulose fibres=and tl'ieexcellent fastness towashing of the aiter' coppered cellulose" dyeings attained therewith.

Disazo divestuff's have been described in U. S. PatentNd-2,1583843 wiiidh oan be produced coupling" tetra'zotis'e'd" 4&4 diaIininOdiphenyl-BiS diglycolic acid of the general formula:

2' mols of 2-amino-5-hydroxvhaphthalene- 7-sulphonic acid or its substitution compounds.

Among others, N-phenyl' compounds are to be understood by this definition, particularly the 2-phenylamino-, 2- (4-methoxyphenylamino) 2- (3'-carboxyphenylamino) or 2 i' -hydroxy ness to washing of their after-coppered cellulose dyeings.

Radicals derived from monobasic organic aliphatic carboxylic acids andalso thosed'erived ire-m carbonicacidi e. radical'sofcarbonic' aici'd half esters come into consideration as acyl radi wis in the 2' -'(4 acylaniino-phefiylamirfo)'-5- hydroxynaphthalene-7-sulphonic acidsusableab cording to the present invention. However, to ensure th'atthe dyestuffs acco'rding'ti the present higher molecular acyl radicalsareto 'b'avoided. As suitable radicals may be named: radicals of lower fatty acids (lower alcoyl' radicals) and the alkoxy carbonyl radicals derived from lower invention are sufficiently water soluble";-

alcohols; particularly suitable;- also arethts a'a rived from alkoxy' substituted lower alcohols The coupling of the 2-(4"-acyl'amihophenlf amino) -5-hydroxynaphtha-lene-'T-suIphUnic a id with the tetrazo component usable according to this invention takes place advantageously in aqueous solution or suspension in the presence of sodium carbonate and a small excess er the couplingcomponent:

I-hthe form of their alkali salts; the disazo dye stuffs' according-to thisinvention are dark powclers which dissolve in water and in concentrated sulphuric acid with a pure blue" colour. It is often advantageous to mix' them with alkali salts of phosphoric acid, e. sodium pyrophosphate, to increase their water solubility. As already described abovejthy dye cellulose fibres from a 'bath contaiiiingGlaubers salt in pure blue shades and on aftel-coppering produce very pure cellulose dyeings which are fast to light and washing.

The direct cellulose dyeings can be coppered either il'L'iZhQdyBbath or afresh bath Withthausual copper salts, e. g. with copper sulphate or copper acetate in neutral or weakly: acid aqueous solu"- tiorr. If desired, copper compounds which are stable-to alkali can also be used such as are obtained'for example by reacting copper sulphate with sodium tartrate in asoda alkaline bath.

The following. examples illustrate the invention without limiting it in anyway. VVhere not" other v'li'se 'stated, parts are given asp'arts by w t; and" thetemperatur'es are in" de rees centigrade.

Example 1- 33.2? partsof 4.4 diaminodiphenyl-3.3- dig-lycolic acid in' the form of its disodium salt aradissolved irr'500 parts of water at 20 and cooled to 0 by the addition of ice. parts of con afterwards 1' 8j parts" ofsofdium nitrite as" 307 hemm d y rochl ac d. an mm d tel volume obtained, is added and the disazo dyestuffs of the formula:

being treated with copper salts and they have excellent fastness to washing and light.

omc ONHC -NH- 03H H088 -NH NHCOCH| N=N N=N 1 I OH con, OCH; H

coon OOH phenylamino) hydroxynaphthalene 7 sulphonic acid, 79.8 parts of 2-(4'-propionylaminophenylamino) -5 hydroxynaphthalene '7 sulphonic acid, 82.6 parts of 2-(4'-butyrylaminopheny1amino)-5 hydroxynaphthalene 7 sulphonic acid or 84.0 parts of 2-(4-chloracetylamino-phenylamino) -5-hydroxynaphthalene-7 sulphonic acid are used and otherwise the same procedure is followed, similar dyestufis are obtained which produce pure blue dyeings with the same excellent fastness properties.

Example 2 33.2 parts of 4.4-diaminodiphenyl-3.3-diglycolic acid are tetrazotised as described in Example l and then coupled with an aqueous solution of 89.2 parts of 2-(4carbomethoxyethoxyaminophenylamino) -5 hydroxynaphthalene 'l sulphonic acid and 64 parts of sodium carbonate.

It has a very good 1 11', in the above example, the 89.2 parts of 2-H carbomethoxyethoxy aminophenylamino) -5-hydroxynaphthalene-'T-sulphonic acid are replaced by 92.0 parts of 2-(4-carbethoxyethoxyamino phenylamino) -5 hydroxynaphthalene- 7-sulphonic acid, 83.1 parts of 2- (4-carbethoxyamino phenylarnino) -5-hydroxynaphthalene-7- sulphonic acid, dyestuffs with almost the same shades and fastness properties are obtained.

Example 3 1 part of the disazo dyestuff obtained according to Example 2 and 2 parts of soda are dissolved in a dye bath containing 3000 parts of water. 100

- parts of cotton are entered at 40-50", the bath is heated to 90-95 within 30 minutes, 30 parts of sodium sulphate are added and dyeing is performed for minutes at this temperature. The dyebath is then completely exhausted. The dyed goods are rinsed cold and after-treated for 30 minutes in a fresh bath containing 2 parts of crystallised copper sulphate in 2000 parts of water and 2 parts of 30% acetic acid. The goods are rinsed and dried in the usual way. The cotton is dyed in clear blue shades which are excellently fast to washing and light.

What I claim is:

l. A disazo dyestuff corresponding to the general formula:

R-NHGNH 40in Ems NH-NHR l V ()H com on, on

coon OOH The next day the disazo dyestufi of the formula:

CHzOCHaCHaOCONH-O-NH -SOsH OH (59H:

door:

is precipitated at 80 with 2% of common salt, filtered 01f, washed with 2% salt solution at and dried. The dyestufi is a dark powder which SOzH OCH:

dissolves in water and concentrated sulphuric acid with a blue colour. It dyes natural or regenerated cellulose fibres in pure blue shades. The shade of the dyeings is hardly altered on 13-0 O-NHONH SO3H OH 0 c 0 (5 C H: O H

C O OH wherein R represents a low molecular aliphatic carboxylic acid acyl radical.

NH-O-NHC o o craonlocnz 2. A disazo dyestuff corresponding to the general formula:

OCH:

( JOOH wherein A represents a low molecular alkyl radical.

3. A disazo dyestuff corresponding to the general formula:

NHNH-C 0-13 wherein 13 represents a low molecular alkoxy radical.

4. A disazo dyestuff corresponding to the formula:

CHsCONHQ-NH --so311 HOgS- T -NH-O-NHCOCH11 on ten, OCHa OH coon OOH 5. A disazo dyestufi corresponding to the formula:

omcmcmo ONHONH s03 H038 -NH NHC 0-CHz-CH2-CHa on $011, $011, H

6. A disazo dyestuff corresponding to the formula:

omoomomoooNnONn $0311 H038 NHONHcooomomo CH3 N=N N=N on (5011: 6on2 on 00011 boot:

7. A disazo dyestuff corresponding to the formula:

CzHtOCHsCHxOC ONH-QNH 03H H038 NHONHoooomoHm 01m N=NC QN=N on H: on, H

to i

$0011 coon 8. A dlsazo dyestufl corresponding to the formula:

CIHIOOONH-ONH 01H H038 NH-O-NHC O O 01H.

H OH: H: H

0 (100B 30 on WERNER BOSSARD.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,158,843 Taube et al May 16, 1939 2,384,419 Fleischhauer et a1. Sept. 4, 1945 FOREIGN PATENTS Number Country Date 261,856 Switzerland Sept. 1, 1949 

1. A DISAZO DYSTUFF CORRESPONDING TO THE GENERAL FORMULA: 